EP0961157A2 - Electrochromic device with a counter electrode of lithium niobate - Google Patents

Abstract

Electrochromic systems with a layer structure containing a layer of conductive electrochromic polydioxythiophen and an ionic reservoir layer consisting of a mixed oxide of lithium with a Sub-Group V metal. Electrochromic systems with a layer structure, in which one layer consists of electrically conductive, electrochromic polydioxy-thiophen (PDOT) and another layer consists of an ionic reservoir of formula LiMeO3 (I), in which Me = a Sub-Group V metal .

Description

The present invention relates to electrochromic arrangements with controllable Translucency, their manufacture and their use.

So far, windows of vehicles can not be transparent for electromagnetic Radiation are regulated. So far, phototropic glasses have only been found as spectacle lenses Use and have only a relatively small change in transmission. Windows on buildings have so far been used with curtains, shutters, shutters or other movable mechanical elements darkened. Electrochromic devices can therefore be used in a variety of ways. So in summary mentioned as examples:

1. Vehicle glazing (window panes or car sun roofs)

An electrochromic device is suitable as sun or glare protection in motor vehicles. Front, side and rear glazing or glass roofs can be included become. The degree of darkening can be adjusted zone by zone and continuously to the needs of the driver to the position of the sun and the current driving situation become. Integration into a computer-controlled control system is possible. A Combination of an active element with a laminated glass unit is also possible, like applying a film system to the safety windows.

The permeability of the panes can be controlled manually or automatically, resulting in effective glare protection when driving at night, automatic adjustment the brightness level when entering and exiting tunnels and car parks and for protection against burglary and theft of the parked vehicle by prevention insight into the car interior can be used. An excessive one Warming of the interior in summer, especially when the vehicle is parked can be prevented (cf. EP-A 0 272 428).

2. Building glazing (electrochromic window)

smart window"). Somit kann ein elektrochromes System zur Regulierung und Begrenzung der notwendigen Energie zur Gebäudeklimatisierung beitragen.In buildings, electrochromic arrangements are suitable for darkening side windows and skylights of buildings, living rooms, work rooms or greenhouses as controllable sun protection (visible spectral range) and heat protection (IR range) as well as visual protection (visible spectral range). To protect against break-ins, glazing of bank counters or shop windows can be darkened at the push of a button. Glass doors can be made visible automatically when people approach to avoid injuries. The ability to create almost all colors also allows the glazing to be incorporated into the facade of a building. The energy consumption for large-scale control of window transparency is low, especially if the memory effect of the system can be used and energy is only used in the switchover phase. A combination with thermal insulation glazing (K glass) is very well suited to ensure dynamic control of the sun's radiation through a window (

smart window "). Thus, an electrochromic system for regulating and limiting the energy required for building air conditioning can contribute.

The system can also be powered by solar modules. A photosensitive sensor can determine the degree of sun exposure and thus control the degree of light transmission.

3. Display elements

Due to the attractive color design and the large-scale display any contours, e.g. B. letters, numbers, characters and symbols (by suitable structuring techniques can be produced) is interesting for advertising Medium available. Decorative and informative effects are easily possible.

In addition to the possibility of arranging the system between glass panes, there is also the alternative to two or just a transparent plastic film as a carrier use. This creates poster-like advertising material with changeable information realizable.

Electrochromic devices can be used for small display elements such as dials of clocks or measuring instruments, displays for a wide variety of applications and for large display elements such as traffic signs, advertising pillars, advertisements be used at train stations, airfields or with parking guidance systems. The stake as a variable line boundary system (field boundaries etc.) in sports halls is also possible.

Use is generally possible where information is made visible should be.

4. Optics

In optics, the use of electrochromic systems is both in combination with Glasses, lenses and filters other optical devices as well as the only actively used Component possible. The application as cross-fade protection for optical Detection systems are also possible. As a controllable filter system for photographic The system is also suitable for processes.

5. Mirror

An electrochromic device can also be used as a dimmable mirror, e.g. B. in the automobile can be used as an exterior or rearview mirror, which can be created by electrical voltage can be darkened and thus by glare Headlights of other vehicles are prevented (see, for example, US-A 3,280,702, US-A 4,902,108, EP-A 0 435 689, US-A 5 140 455). A disadvantage of systems after State of the art (solution systems) is the color inhomogeneity after a long time Operation (segregation), especially with mirrors of large dimensions (e.g. truck mirrors). An increase in the viscosity of the solution system by adding polymer Thickeners are described (e.g. US-A 4 902 108).

6. EMI shielding

An electrochromic device can also act as a variable filter element for modulation electromagnetic radiation used in certain wavelength ranges become.

Electrochromic devices usually consist of a pair of glass or Plastic discs, one of which is mirrored in the case of a mirror. A Side of these discs is with a translucent, electrically conductive layer, e.g. B. Indium Tin Oxide (ITO) coated. These disks become a cell constructed by being electrically conductive with their facing each other coated side are fixed, the cell between the washers contains electrochromic system. It is tightly closed. Over the conductive layer the two disks can be electrically contacted and controlled separately.

In the electrochromic known from the prior art cited above Solution systems are such pairs of redox substances in a solvent contain the colored positively or negatively charged after reduction or oxidation Form radicals that are chemically reactive. Examples of this have been for a long time known viology systems.

As a pair of redox substances, one is reducible and one is oxidizable Substance used. Both are colorless or only slightly colored. Under the influence one voltage is reduced, the other oxidizes, with at least one becoming colored. After switching off the voltage, the both original redox substances back, whereby discoloration or Color brightening occurs.

From US-A 4 902 108 it is known that such pairs of redox substances are suitable are in which the reducible substance at least two chemically reversible Reduction waves in the cyclic voltammogram and the oxidizable substance accordingly has at least two chemically reversible oxidation waves. Systems This type is mainly used for dimmable car rear-view mirrors. Because it these are solution systems, they are used in electrochromic applications Windows are not considered under normal circumstances.

Systems are also known in which the actual electrochromic redox couple is dispersed in a polymer matrix (see e.g. WO-A 96/03475). The unwanted The effect of segregation is suppressed.

Combinations of inorganic electrochromic components, such as. B. WO ₃ , NiO or IrO ₂ are also known and can be used as components in an electrochromic window (see, for example, US Pat. No. 5,657,149, Electronique International No. 276, 16 (1997)).

These inorganic electrochromic components can only be applied to the conductive substrate by vapor deposition, sputtering or by sol-gel technology. This leads to systems of this type becoming very expensive to manufacture. In an effort to replace an inorganic component with an organic polymer component, e.g. B. electrochromic systems based on the electrically conductive polymer polyaniline (PANI) and WO ₃ have become known as complementary electrochromic materials (see, for example, BP Jelle, G. Hagen, J. Electrochem. Soc., Vol. 140, Non. 12, 3560 (1993 )). Attempts have also been made to use systems without an inorganic component, the ITO or SnO ₂ layer (counter electrode) serving as complementary electrochromic components to substituted poly (3,4-alkylenedioxythiophenes) (US Pat. No. 5,187,608) .

However, it turns out that such electrochromic arrangements are unsuitable for a sufficient number of switching cycles without changing the device properties to ensure.

Me

für ein Metall der V. Nebengruppe des Periodensystems nach Mendelejew steht, bevorzugt für V, Nb und Ta.

The present invention relates to an electrochromic arrangement in a layer structure, characterized in that one layer is an electrically conductive, electrochromic polydioxythiophene and another layer is an ion store of the formula LiMeO ₃ is what

Me

stands for a metal of the V subgroup of the Mendeleev periodic table, preferably for V, Nb and Ta.

The following ion storage layer is very particularly preferably used:
LiNbO ₃ .

Nickeloxide

TiO₂

CeO₂

V₂O₅

Nb₂O₅

Ta₂O₅

darstellen.The ion storage can also be a mixture of compound (1) with other metal oxides such as

Nickel oxides

TiO ₂

CeO ₂

V ₂ O ₅

Nb ₂ O ₅

Ta ₂ O ₅

represent.

The ion storage device in the construction according to the invention thus consists of a Metal oxide compound or a mixture of metal oxides. The ion storage layers can already contain a Li salt during their production or even first subsequently be loaded electrochemically with Li ions.

The compounds of the formula (I) are generally known compounds or can be prepared by generally known methods of inorganic chemistry, as described, for example, in N. Özer, CM Lampert, Solar Energy Materials and Solar Cells 39 (1995), 367 for the example LiNbO ₃ .

The electrochromic arrangement according to the invention thus contains at least one inorganic Ion storage layer. This can be done either by a sol-gel process, by vapor deposition / sputtering or electrochemically on an electrically conductive Substrate can be applied to improve the conductivity with a Metal grid can be provided. It can also be nano-particles, which can be applied using a casting technique.

aufgebaut, in der

A¹ und A²

unabhängig voneinander für gegebenenfalls substituiertes (C₁-C₄)-Alkyl stehen oder zusammen gegebenenfalls substituiertes (C₁-C₄)-Alkylen bilden, und

n

für eine ganze Zahl von 2 bis 10.000 vorzugsweise 5 bis 5 000 steht,

in Gegenwart von Polyanionen.The polydioxythiophenes are cationically charged and consist of structural units of the formula (II)

built in the

A ¹ and A ²

independently represent optionally substituted (C ₁ -C ₄ ) alkyl or together form optionally substituted (C ₁ -C ₄ ) alkylene, and

n

represents an integer from 2 to 10,000, preferably 5 to 5,000,

in the presence of polyanions.

worin

R₁ und R₂

unabhängig voneinander für Wasserstoff, gegebenenfalls substituiertes (C₁- C₁₈)-Alkyl, vorzugsweise (C₁-C₁₀)-, insbesondere (C₁-C₆)-Alkyl, (C₂-C₁₂)-Alkenyl, vorzugsweise (C₂-C₈)-Alkenyl, (C₃-C₇)-Cycloalkyl, vorzugsweise Cyclopentyl, Cyclohexyl, (C₇-C₁₅)-Aralkyl, vorzugsweise Phenyl-(C₁-C₄)-alkyl, (C₆-C₁₀)-Aryl, vorzugsweise Phenyl, Naphthyl, (C₁-C₁₈)-Alkyloxy, vorzugsweise (C₁-C₁₀)-Alkyloxy, beispielsweise Methoxy, Ethoxy, n- oder iso-Propoxy, oder (C₂-C₁₈)-Alkyloxyester steht und

R₃, R

₄ unabhängig voneinander für Wasserstoff, aber nicht beide gleichzeitig, mit mindestens einer Sulfonatgruppe substituiertes (C₁-C₁₈)-Alkyl, vorzugsweise (C₁-C₁₀)-, insbesondere (C₁-C₆)-Alkyl, (C₂-C₁₂)-Alkenyl, vorzugsweise (C₂-C₈)-Alkenyl, (C₃-C₇)-Cycloalkyl, vorzugsweise Cyclopentyl, Cyclohexyl, (C₇-C₁₅)-Aralkyl, vorzugweise Phenyl-(C₁-C₄)-alkyl, (C₆-C₁₀)-Aryl, vorzugweise Phenyl, Naphthyl, (C₁- C₁₈)-Alkyloxy, vorzugweise (C₁-C₁₀)-Alkyloxy, beispielsweise Methoxy, Ethoxy, n- oder iso-Propoxy oder (C₂-C₁₈)-Alkyloxyester steht.

n

für eine Zahl von 2 bis 10 000, vorzugsweise 5 bis 5 000 steht.

Preferred cationic polydioxythiophenes are composed of structural units of the formula (IIa) or (IIb)

wherein

R ₁ and R ₂

independently of one another for hydrogen, optionally substituted (C ₁ -C ₁₈ ) -alkyl, preferably (C ₁ -C ₁₀ ) -, in particular (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₁₂ ) -alkenyl, preferably ( C ₂ -C ₈ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C ₇ -C ₁₅ ) aralkyl, preferably phenyl (C ₁ -C ₄ ) alkyl, (C ₆ -C ₁₀ ) aryl, preferably phenyl, naphthyl, (C ₁ -C ₁₈ ) alkyloxy, preferably (C ₁ -C ₁₀ ) alkyloxy, for example methoxy, ethoxy, n- or iso-propoxy, or (C ₂ - C ₁₈ ) alkyloxy ester and

R ₃ , R

₄ independently of one another for hydrogen, but not both at the same time, with (C ₁ -C ₁₈ ) -alkyl substituted with at least one sulfonate group, preferably (C ₁ -C ₁₀ ) -, in particular (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₁₂ ) alkenyl, preferably (C ₂ -C ₈ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C ₇ -C ₁₅ ) aralkyl, preferably phenyl (C ₁ - C ₄ ) alkyl, (C ₆ -C ₁₀ ) aryl, preferably phenyl, naphthyl, (C ₁ - C ₁₈ ) alkyloxy, preferably (C ₁ -C ₁₀ ) alkyloxy, for example methoxy, ethoxy, n- or iso-propoxy or (C ₂ -C ₁₈ ) alkyloxy ester.

n

represents a number from 2 to 10,000, preferably 5 to 5,000.

worin

R₃

die obengenannte Bedeutung hat.

n

für eine ganze Zahl von 2 bis 10 000, vorzugsweise 5 bis 5 000 steht.

The electrochromic device structure according to the invention very particularly preferably contains at least one electrically conductive, electrochromic cationic or neutral polydioxythiophene of the formulas (II a-1) and / or (II b-1)

wherein

R ₃

has the meaning given above.

n

represents an integer from 2 to 10,000, preferably 5 to 5,000.

The anions of polymeric carboxylic acids, such as polyacrylic acids, serve as polyanions. Polymethacrylic acids, or polymaleic acids and polymeric sulfonic acids, such as polystyrene sulfonic acids and polyvinyl sulfonic acids. These polycarbonate and sulfonic acids can also copolymers of vinyl carbon and vinyl sulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.

The anion of the polystyrene sulfonic acid is particularly preferred as the counter ion.

The molecular weight of the polyacids providing the polyanions is preferably 1000 to 2,000,000, particularly preferably 2,000 to 500,000. The polyacids or their alkali salts are commercially available, e.g. Polystyrene sulfonic acids and Polyacrylic acids, or can be produced by known processes (see e.g. Houben Weyl, Methods of Organic Chemistry, Vol. E 20 Macromolecular Substances, Part 2, (1987), p. 1141 and others).

Instead of that for the formation of the dispersions from polydioxythiophenes and Free polyacids required for polyanions, one can also use mixtures of alkali salts the polyacids and corresponding amounts of monoacids.

In the case of the formula (IIb1), the polydioxythiophenes carry positive and negative charges in the structural unit. The preparation of the polydioxythiophenes is for example in EP-A 0 440 957 (= US-A 5 300 575).

The polydioxythiophenes are obtained by oxidative polymerization. Thereby they get positive charges that are not shown in the formulas because of their number and their position cannot be determined properly.

The present invention accordingly relates to an electrochromic device structure electrically conductive poly (3,4-ethylenedioxythiophene) derivatives as cathodic coloring electrochromic polymers and suitable ion storage layers for Li-ion. A gel electrolyte consisting of a cross-linked or uncross-linked Polymer, a Li salt and a certain amount of a solvent between the electrochromic polymer layer and the ion storage layer. Of the schematic structure is shown in Fig. 1, principle I).

Legend from Fig. 1:

1.2:

Substrate

3.4:

electrically conductive coating, one of which can act as a mirror

5:

Electrochromic polymer e.g. PEDT / PSS

6:

Ion storage layer

7:

Gel electrolyte (cross-linked or non-cross-linked)

8.9:

fine mesh net made of metal (optional)

The electrochromic polymer layer is transparent in the doped state. This leaves by electron uptake (reduction) at the cathode while increasing the Convert absorbance in the visible range of the spectrum to a colored form. The oxidation taking place on the opposite side (anode) is marked with a Exchange reaction of the ion storage layer linked with Li ions. This reaction however, hardly contributes to the coloring, so that it does not interfere with the weight.

The present invention therefore relates to an electrochromic solid phase system, containing at least one redox-active, electrically conductive polymer the substance class of the poly (3,4-ethylenedioxythiophene) derivatives which are used for Processability from solution may have added polystyrene sulfonate, or in carry a solubilizing sulfonate group on one side chain. This polymer layer is preferably applied from an aqueous solution, after evaporation the solvent is the solid, dry polymer film on the substrate remains. However, it should also be able to be applied by screen printing. As substrates are preferably an electrically conductive, transparent glass or film system used, with a layer of indium tin oxide (ITO), doped with fluorine Tin oxide (FTO, K glass), undoped tin oxide or a layer of finely divided Silver serves as the electrode. It is also possible that an electrode side from a Metal layer (such as Al, Cu, Pd) is no longer transparent (at Use in the mirror). The gel electrolyte contains at least one polymer (e.g. Polyethylene oxide, PMMA), at least one Li salt (e.g. Li triflate, Li perchlorate) and at least one solvent (e.g. propylene carbonate).

The present invention relates to use as electrochromic Device in the building or architectural glazing and as vehicle glazing or sunroof can also be used as a display element, as electrochromic mirror (e.g. auto-dimmable automotive rearview mirror) also the Use in various optical elements.

For use as a mirror, one of the two electrodes can be vapor-deposited or electrochemically deposited metal coating, e.g. Aluminum, Silver, copper, platinum, palladium, rhodium.

The present invention also relates to an electrochromic system, in which the coloring electrochromic polymer compound simultaneously as their own Electrode acts, leaving only a conductive coating of ITO, fluorine doped Tin oxide or a metal is necessary. (see Fig. 1, Principle II))

Legend of Fig. 1, principle II:

1.2:

Substrate

4th

: electrically conductive coating that can also act as a mirror

5:

Electrochromic polymer

6:

Ion storage layer

7:

Gel electrolyte (cross-linked or non-cross-linked)

8.9:

fine mesh net made of metal (optional)

The electrochromic structure according to the invention is particularly preferred characterized in that a combination with a heat protection glass (commercially available for architectural glazing purposes) explicitly as a positive development characteristic for energy saving measures of sun-drenched rooms is possible. More explicit Electrodes made of other material are therefore not necessary because of the heat protection layer limits the passage of IR radiation and at the same time by the electrical conductivity takes over the electrode function in the electrochromic structure.

The electrochromic structure according to the invention is also characterized by that the electrochromic layer also IR radiation in certain areas can absorb and thus limit the heat transfer through the pane can.

The electrochromic layer structure according to the invention is part of an electrochromic Suitable device. The inventive device is used in an electrochromic device electrochromic layer structure as a medium with variable transmission, i.e. the light transmittance changes under the influence of an electrical voltage of the system by moving from a colorless to a colored state transforms. The present invention accordingly further relates to electrochromic Devices containing an electrochromic device structure according to the invention. Applications of this electrochromic device are in architectural glazing and in means of transport e.g. as a window pane, car sun roof, Automotive rear-view mirror, display or as an optical element, or as a component of information display units such as instrument displays in vehicles of any Art.

In the event that the electrochromic device is an electrochromic display device is at least one of the two conductive layers or both in electrical separate segments that are contacted individually.

However, only one of the two plates can be conductively coated and divided into segments. The segments can be separated, for example, by mechanical removal of the conductive layer, for example by scratching, scraping, scraping or milling, or by chemical means, for example by etching using, for example, a hydrochloric acid solution of FeCl ₂ and SnCl ₂ . This removal of the conductive layer can be locally controlled using masks, for example those made of photoresist. However, the electrically separated segments can also be produced by targeted, for example by means of masks, application, for example sputtering or printing, the conductive layer. The segments are contacted, for example, by means of fine strips of conductive material, with which the segment is electrically conductively connected to a contact on the edge of the electrochromic device. These fine contact strips can either consist of the same material as the conductive layer itself and can also be produced, for example, when it is divided into segments, as described above. However, they can also be made of another material such as fine metallic conductors, for example of copper or silver, for example to improve the conductivity. A combination of metallic material and the material of the conductive coating is also possible. These metallic conductors can, for example, either be applied in fine wire form, for example glued on, or else be printed on. All of the techniques described above are generally known from the manufacture of liquid crystal displays (LCD).

In the case of displays, the displays according to the invention can be transmitted or can also be considered reflectively via mirroring.

In the event that the electrochromic device is an electrochromic window, on one or both electrodes have a fine mesh of metal vapor deposited. This serves to improve the surface conductivity of the substrates and is at large areas are an advantage to achieve a uniform coloring.

The electrochromic device structure according to the invention preferably contains at least one transparent electrically conductive coating on a substrate (glass or plastic), consisting of indium tin oxide (In ₂ O ₃ : SnO ₂ (ITO)), tin oxide (SnO ₂ ), fluorine -doped tin oxide (SnO ₂ : F; FTO or "K-glass", "heat protection glass"), antimony-doped tin oxide, antimony-doped zinc oxide, aluminum-doped zinc oxide or a transparent metal film with a sufficiently thin layer thickness, e.g. silver coating (heat protection glass, e.g. ®PLANITHERM).

Other conductive polymers such as optionally substituted polythienyls, Polypyrroles, polyanilines, polyactetylene or polythiophenes can be used.

The actual electrochromic polymer is in the device structure according to the invention also preferably as its own conductive electrode material instead of one of the use the above-mentioned conductive coatings.

Indium-tin oxide (In ₂ O ₃ : SnO ₂ (ITO)), tin oxide (SnO ₂ ), fluorine-doped tin oxide (SnO ₂ : F; FTO, "K glass", "heat protection glass") are very particularly preferred. or a transparent silver coating with a sufficiently thin layer (heat protection glass) is used.

If one of the panes is mirrored, this conductive layer can also be used become. Silver, aluminum, copper, platinum, Palladium and rhodium are used.

Polymer (vernetzt oder unvernetzt)

Li-Salz

Lösungsmittel oder Lösungsmittelgemisch

The electrochromic structure according to the invention preferably contains a transparent gel electrolyte, which consists of the following components:

Polymer (cross-linked or non-cross-linked)

Li salt

Solvent or solvent mixture

Polymethyl methacrylate (PMMA) and polyethylene oxide are the preferred polymers (PEO), polyacrylonitrile (PAN), poly (N, N-dimethylacrylamide), poly (2- (2-methoxyethoxy) ethoxy) phosphazene, Poly (oxymethylene-oligo (oxyethylene)), polyethylene glycols (PEG), polypropylene glycols (PPG) or polymers based on Polyepichlorohydrin or polyether and mixtures in question. Also copolymers such as ethylene oxide-propylene oxide (EO / PO) copolymer or oxymethylene-bridged Polyethylene oxides.

Polyethers and polyethylene oxides are particularly preferably used.

Photocrosslinkable polymer systems based on are also particularly preferred Acrylates such as Polyethylene glycol 400 diacrylate, polyethylene glycol 400 dimethacrylate, Polyethylene glycol 600 diacrylate, polyethylene glycol 600 dimethacrylate, Polyethylene glycol methacrylate, tripropylene glycol diacrylate, tripropylene glycol monomethyl ether acrylate, Trimethylolpropane triacrylate, ethylene glycol dimetharcylate, Hydroxyethyl methacrylate (HEMA), hexanediol diacrylate, dianol diacrylate, Tetraethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Butyl methacrylate and the acrylates Roskydal® UA VP LS 2258 or Roskydal® UA V 94/800 from Bayer AG and their acrylate precursors. The Photocrosslinkable polymer systems are said to be used in the presence of the Solvent and the Li salt with the help of a light activation using a common photoinitiators such as ®Darocure 1173, 1116 or ®Irgacure 184 (from E. Merck KGaA, Darmstadt) also between thick glass plates covered with a transparent electrical coating are to be cured. The exposure takes place after filling the cell by irradiation with a suitable one Lamp (e.g. UV lamp such as Hg or Xe lamp). The curing of polymer systems by electron beam curing is also in the systems mentioned possible.

Polymer systems that are thermal and catalytic are also particularly preferred about isocyanate groups with OH-functional polyether compounds, such as. B. polyether polyols can be crosslinked and form polyurethanes. Also polyurethane with different soft segments such as B. polytetramethylene glycol or Polypropylene glycol.

Modified siloxanes from e.g. gamma-glycidylpropyltrimethoxysilane. It can be z. B. modified by polypropylene oxide Act variants.

The gel electrolytes can also be organic and / or inorganic fillers or Additives included. The usual additives such as Thermal stabilizers, optical brighteners, flame retardants, flow aids, fire retardants, Colorants, pigments, fillers or reinforcing materials, finely divided minerals, Fibers, chalk, quartz powder, glass, aluminum oxide, aluminum chloride and Carbon fibers can be added in usual amounts. The function of a Spacers can e.g. of glass balls, polymer particles, silica gel or grains of sand with a defined size if necessary.

LiClO ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiCl, LiPF ₆ are possible as preferred Li salts.

LiClO ₄ , LiCF ₃ SO ₃ and LiN (SO ₂ CF ₃ ) ₂ are very particularly preferred.

Propylene carbonate, ethylene carbonate, Acetonitrile and γ-butyrolactone and mixtures thereof in question.

Propylene carbonate and ethylene carbonate are very particularly preferably used.

Glass or various substrates are used as substrates in the electrochromic structure according to the invention Types of plastic used.

In general, transparent substrates of any kind are preferred.

As particularly preferred materials in addition to glass, especially heat protection glass when used as an electrochromic window, (in layer thicknesses of 10 µm at flexible glass, thin glass "up to 3 cm) are polyester (for example polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)), various types of polycarbonate (for example ®Makrolon, APEC-HT), polysulfones, polyimides and polycycloolefins. The polymeric substrate can The substrate can also be curved so that the layer structure adapts to the shape of the base. After the overall electrochromic system has been built up, a flexible plastic substrate can also be applied to various substrates, such as curved glass, for example. be laminated on or glued on.

The plastic substrates can additionally with barrier layers against water and Be provided with oxygen.

TiO _x , SiO _x on polyester, for example polyethylene terephthalate, Du Pont (see packaging films) or fluorinated polymers and possible combinations thereof, and also barrier layers based on inorganic-organic hybrid systems are preferred.

The electrochromic structure according to the invention can be flexible in design Foil system as a complete electrochromic composite system on the safety windows be laminated or glued by cars. He can also in the Cavity of a laminated glass pane system integrated into the architectural glazing become.

The control mechanism of the electrochromic structure is based on the reversible electrochemical Doping of the electrochromic polymer, which is reflected in strong

Color changes, for example, from colorless to blue. The construction is done with defined voltages.

The reduction and oxidation processes in the electrochromic according to the invention In general, they are built up by electron acceptance or release at the Cathode or anode, preferably a potential difference between the electrodes from 0.1 to 5 V, very particularly preferably 0.1 to 3 V. After Switching off the electrical potential can cause the previously achieved coloring can be maintained for a long time (memory effect), so that one with minimal Energy consumption can achieve permanent coloring. By briefly A polarity reversal and thus discoloration can be achieved spontaneously.

The electrochromic structure according to the invention is also suitable for larger areas characterized that a supply by means of solar modules is possible.

In addition, it was found that the electrochromic polymer film did not only arise in situ the electrically conductive substrate must be generated, but from ecological harmless aqueous solution by a casting technique, by spin coating / dip coating, can be applied by screen printing or by spraying. This method is particularly suitable for large-area systems.

For better wetting of the substrates, a wetting agent (e.g. Fluorosurfactant) are added.

Examples: example 1 Application of an electrochromic polymer to an ITO substrate

wird aus wäßriger Lösung, die noch Isopropanol enthält, mit einer Lackschleuder 4 mal mit je 15 Sekunden bei einer Umdrehungsgeschwindigkeit von 1500 U/min. auf die elektrisch leitfähige Seite einer ITO-Glasscheibe (Fa. Merk-Balzers, Lichtenstein, Oberflächenwiderstand <15 Ω/sq) aufgebracht. Während dem Aufbringen wird mittels eines Föns das Lösungsmittel abgedampft The polymer Baytron® P (aqueous dispersion of the conductive polymer PEDT / PSS, polyethylene dioxythiophene polystyrene sulfonate from Bayer AG)

is from aqueous solution, which still contains isopropanol, with a spin coater 4 times with 15 seconds each at a speed of rotation of 1500 rpm. applied to the electrically conductive side of an ITO glass pane (Merk-Balzers, Lichtenstein, surface resistance <15 Ω / sq). During the application, the solvent is evaporated using a hair dryer

A transparent, only slightly bluish-colored polymer film is obtained. A measurement of the layer thickness with a profilometer gave a value of 0.6 µm.

Example 2 Apply Baytron® P to K glass

Baytron® P (as in Example 1) is extracted from an aqueous solution using a paint spinner 4 times with 15 seconds each at a rotation speed of 1500 rpm. on the electrically conductive side of a K-glass pane (heat protection pane from flat glass, surface resistance ∼ 20 Ω / sq). While the application is evaporated using a hair dryer.

A transparent, only slightly bluish-colored polymer film is obtained. A measurement of the layer thickness showed a value of 0.6 µm.

Example 3 Application of an ion storage layer made of lithium niobate to K glass

There are 1.5 g of niobium V-ethoxide and 0.259 g of lithium ethoxide in 10 ml each dry ethanol dissolved. These two will each be 0.5 molar solutions Stir for 1 hour at room temperature before combining. Subsequently the mixture obtained is stirred for a further 1.5 hours at room temperature.

The sol solution obtained in this way is applied to the conductive side of K glass panes coated (10 sec. at 1500 rpm). Then the layers are 2 hours annealed at 300 ° C for a long time. The layers obtained are closed as an ion storage layer use.

Example 4 Preparation of a Gel Electrolyte 1

7,0 g Acetonitril

2,0 g Propylencarbonat (trocken)

0,7 g PMMA (M_w ca. 15.000)

0,3 g CF₃SO₃Li (Fa. Aldrich)

The following mixture is generated:

7.0 g acetonitrile

2.0 g propylene carbonate (dry)

0.7 g PMMA (M _w approx.15,000)

0.3 g CF ₃ SO ₃ Li (Aldrich)

After everything is dissolved, the solution is filtered once and is ready for use.

Example 5 Preparation of a gel electrolyte 2

7,0 g Acetonitril

2,0 g Propylencarbonat

0,7 g Polyethylenoxid (PEO; M_w ca. 200.000)

0,3 g CF₃SO₃Li (Fa. Aldrich)

Procedure as in example 4 but with the following weights:

7.0 g acetonitrile

2.0 g propylene carbonate

0.7 g polyethylene oxide (PEO; M _w approx. 200,000)

0.3 g CF ₃ SO ₃ Li (Aldrich)

Example 6 Preparation of a gel electrolyte 3

7.7 g of the unsaturated aliphatic urethane acrylate Roskydal® UA VP LS 2258 (Bayer AG) together with 0.1925 g (2.5% by weight) of Darocure photoinitiator 1173 from Merck, Darmstadt and 0.3 g (3% by weight) of lithium trifluoromethanesulfonate from Aldrich in 2 g of dry 1,2-propylene carbonate from Aldrich. This mixture is pourable and can be cross-linked photochemically, whereby a no longer flowable gel electrolyte can be produced.

Example 7 Manufacture of a gel electrolyte layer; Construction of the electrochromic according to the invention Cell 1

The still uncrosslinked gel electrolyte 3 from example 6 is applied to the ion storage layer from Example 3 applied with a wet film thickness of 200 microns and with a brought into contact electrochromic layer from Example 2. This association is with a belt running speed of 20 m / min under a UV lamp (actual lamp) transported away. This crosslinks the gel electrolyte. You get systems that contain a no longer flowing gel electrolyte and are transparent.

Example 8 (comparison: without ion storage layer) Completion of a complete electrochromic cell 2 and 3

On the conductive side of ITO glasses, gel electrolytes 1 and 2 are made from the Examples 4 and 5 applied evenly and with the Baytron P-coated Sides of glass substrates from Example 1 brought into contact. You get each have an electrochromic layer structure, which is characterized in Example 9.

Example 9 Cycle stability test on electrochromic cells 2 and 3

The electrochromic comparison cells 2 and 3 from Example 8 are each on the ITO layers with 1.6 V DC are briefly contacted before the Polarity of the electrical control changes. One achieves a cyclical one Staining and decolorization of the cell. At the same time, one observes the temporal change in the transmission through the cell. It is found that Arrangements without an additional ion storage layer have no cycle stability (See Fig. 2). This is intended to be improved by the present invention which is demonstrated in Example 10.

Example 10 Cycle stability test on the electrochromic cell 1

The electrochromic cell 1 from Example 7 is in each case on the conductive layers the coated K glasses from Examples 2 and 3 with 2.5 V DC short Time contacted before changing the polarity of the electrical control. This results in cyclical staining and decolorization of the cell. Here one observes at the same time the change in transmission through the cell over time. It is found that arrangements with the lithium niobate ion storage layer a significant improvement in cycle stability compared to previous arrangements (see Examples 8 and 9) (see Fig. 3). Even after relative high number of on and off cycles, there is almost no change in the Properties of the electrochromic arrangement.

Claims (14)

Electrochromic arrangements in a layer structure, characterized in that one layer is an electrically conductive, electrochromic polydioxythiophene and another layer is an ion store of the formula LiMeO ₃ is what

Me

stands for a metal of subgroup V of the periodic table according to Mendeleev.

Electrochromic devices according to claim 1, wherein

Me

stands for Nb.

Electrochromic arrangements according to claims 1 and 2, wherein the following compounds or a mixture of at least two compounds function as ion stores:
LiNbO ₃ , LiVO ₃ , LiTaO ₃ . Electrochromic arrangements according to claims 1 to 3, wherein the following further compounds can be contained in an ion storage layer: TiO ₂ CeO ₂ V ₂ O ₅ Nb ₂ O ₅ Nickel oxides. Electrochromic arrangements according to claim 1, wherein cationic or neutral polydioxythiophenes from structural units of the formula (II)

are built in the

A ¹ and A ²

independently represent optionally substituted (C ₁ -C ₄ ) alkyl or together form optionally substituted (C ₁ -C ₄ ) alkylene, and

n

represents an integer from 2 to 10,000,
and the counterions are polyanions.

Electrochromic arrangements according to claim 5, wherein the cationic or neutral polydioxythiophenes are composed of structural units of the formula (IIa) or (IIb)

wherein

R ₁ and R ₂

independently of one another for hydrogen, optionally substituted (C ₁ -C ₁₈ ) alkyl, (C ₂ -C ₁₂ ) alkenyl, (C ₃ -C ₇ ) cycloalkyl, (C ₇ -C ₁₅ ) aralkyl, (C ₆ -C ₁₀ ) aryl, (C ₁ -C ₁₈ ) alkyloxy or (C ₂ -C ₁₈ ) alkyloxy ester and

R ₃ , R ₄

independently of one another for hydrogen, but not both at the same time, with (C ₁ -C ₁₈ ) alkyl substituted with at least one sulfonate group, (C ₂ -C ₁₂ ) alkenyl, (C ₃ - C ₇ ) cycloalkyl, (C ₇ -C ₁₅ ) aralkyl, (C ₆ -C ₁₀ ) aryl, (C ₁ -C ₁₈ ) alkyloxy or (C ₂ -C ₁₈ ) alkyloxy ester,

n

represents a number from 2 to 10,000.

Electrochromic arrangements according to claim 6, containing cationic or neutral polydioxythiophene of the formula (II a-1) or (II b-1)

wherein
R ₃ and n has the meaning given in claim 5. Electrochromic arrangements according to claims 6 and 7, wherein the Polyanions Anions of polymeric carboxylic acids and / or polymeric Are sulfonic acids. Electrochromic arrangements according to Claims 1 to 8, characterized in that the electrochromic arrangements are at least one transparent contains electrically conductive coating applied to a substrate. Electrochromic devices according to claims 1 to 8, wherein the conductive Electrode material is an electrically conductive polydioxythiophene. Electrochromic arrangements according to claims 1 to 8, wherein one with a Metal mirrored disc (substrate) as a conductive layer for Contacting is used. Electrochromic arrangements according to Claims 1 to 11, characterized in that the electrochromic structure according to the invention contains a transparent gel electrolyte which contains the following components: Polymer (cross-linked or non-cross-linked) Li salt Solvent or solvent mixture. Electrochromic arrangements according to claims 1 to 12, wherein Photo-crosslinkable polymers are used. Electrochromic arrangements according to claims 12 and 13, characterized in that the gel electrolytes are also organic and / or inorganic Contain fillers and / or additives.

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